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Publication numberUS3261782 A
Publication typeGrant
Publication dateJul 19, 1966
Filing dateMar 5, 1964
Priority dateFeb 19, 1963
Publication numberUS 3261782 A, US 3261782A, US-A-3261782, US3261782 A, US3261782A
InventorsDonald J Anderson, Vries Louis De
Original AssigneeChevron Res
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alkylbutyrolactone-alpha-acetic acids
US 3261782 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent M 3,261,782 ALKYLBUTYROLACTONE-oc-ACETIC ACIDS Donald J. Anderson, San Anselmo, and Louis de Vries,

Richmond, Calif., assignors to Chevron Research Company, a corporation of Delaware No Drawing. Filed Mar. 5, 1964, Ser. No. 349,747 2 Claims. (1. 252-57) This application is a continuation-in-part of Donald J. Anderson and Louis de Vries application Serial No. 259,- 722, filed February 19, 1963 (now abandoned).

This invention pertains to lubricating oil compositions having incorporated therein metal-free detergents.

Present day internal combustion engines operate at high speeds and high compression ratios. When used in the so-called city stop-and-go driving, which includes the greater part of the driving conditions for a large percentage of todays automobiles, the internal combustion engines do not reach the most efficient operating temperature. Under city driving conditions, large amounts of partial oxidation products are formed, and reach the crankcase of the engine by blowing past the piston rings. Most of these partial oxidation products are oil-insoluble, tending to form deposits on the various operating parts of the engine, such as the pistons, piston rings, etc. For the purpose of preventing the deposition of these products on the various engine parts, it is necessary to incorporate detergents in the lubricating oil compositions, thus keeping these polymeric products highly dispersed in a condition unfavorable for deposition on metals.

For the most part, the various detergents which are added to crankcase oils to reduce this formation of sludges and varnishes are metal organic compounds, particularly those compounds wherein the metal is linked to an or ganic group through an oxygen atom. Although these metal-containing organic compounds have some effectiveness as detergents for dispersing the precursors of deposits Within the oil itself rather than permitting them to form added deposits on the engine parts, they have the disadvantage of forming ash deposits in the engine. These ash deposits lower engine performance by fouling spark plugs and valves, and contribute to preignition.

It is a particular object of this invention to provide new compounds which are used in the formation of metal-free detergents for lubricating oil compositions.

Therefore, in accordance with this invention, it has been discovered that alkylbutyrolactone-a-acetic acids are new compounds which are useful as intermediates in the formation of amides of alkylbutyrolactone-u-acetic acid. These amides of alkylbutyrolactone-u-acetic acid are effective as detergents in lubricating oil compositions.

The alkylbutyrolactone-ut-acetic acids described herein are useful not only as intermediates in the formation of metal-free detergents, but these alkylbutyrolactone-a-acetic acids are useful as rust inhibitors in lubricating oil compositions.

These acids, which are new compounds, are of the formula o CHCHZCOOH 3,261,782 Patented July 19, 1966 wherein R R and R are hydrogen or alkyl radicals containing a total of from 10 to 300 carbon atoms. The total number of carbon atoms in R R and R is preferably from 10 to 100.

These alkyl butyrolactone-a-acetic acids can be prepared by reacting an olefinic hydrocarbon with dimethyl bromosuccinate to obtain the methyl ester which is then converted to the acid.

The amides of the above-described alkylbutyrolactonea-acetic acid are those derived from ammonia or amines, including aliphatic, cycloaliphatic and aromatic monoamines, polyamines and heterocyclic amines. In any case, the amino group reacting with the carboxyl groups to form the amide must be a primary or secondary amino group.

The resulting amides include those of the formula wherein R R and R are the same as defined hereinabove, and R is hydrogen or the residue of an amine radical having from 1 to 20 carbon atoms, preferably from 2 to 12 carbon atoms, and from O to 10 nitrogen atoms.

Of particular preference as lubricating oil additives are the gamma alkylbutyrolactone-u-acetic acids wherein the gamma alkyl radical contains from 10 to 300 carbon alkyl radical containing from 10 to 300 carbon atoms, and atoms; that is, wherein R in the above formula is an R and R are hydrogen.

Lubricating oils which can be used as base oils when these alkylbutyrolactone-a-acetic acids are used therein include a wide variety of lubricating oils, such as naphthenic base, paraifin base, and mixed base lubricating oils, other hydrocarbon lubricants, e.g., lubricating oils derived from coal products, and synthetic oils, e.g., alkylene polymers (such as polymers of propylene, butylene, etc., and mixtures thereof), alkylene oxide-type polymers (e.g., propylene oxide polymers) and derivatives, including alkylene oxide polymers prepared by polymerizing the alkylene oxide in the presence of water or alcohols, e.g., ethyl alcohol, di-car'boxylic acid esters (such as those which are prepared by esterifying such dicarboxylic acids as adipic acid, azelaic acid, suberic acid, sebacic acid, alkanol succinic acid, fumaric acid, maleic acid, etc., with alcohols such as butyl alcohol, hexyl alcohol, Z-ethylhexyl alcohol, dodecyl alcohol, etc.), liquid esters of acids of phosphorus, alkyl benzenes (e.g., monoalkyl benzene such as dodecyl benzene, tetradecyl benzene, etc.) and dia'lkyl benzenes (e.g., n-nonyl-Z-ethylhexy-l benzene), polyphenyls (e.g., 'biphenyls and tenphenyls), alkyl biphenyl ethers, compounds of silicon, e.g., tetraethyl silicate, tetraisopropyl silicate, tetra(4-methyl-2-tetraethyl) silicate, hexyl-(4- methyLZ-pentoxy) disiloxane, poly(-met hyl) siloxane, poly(methylpheny-l) siloxane, etc.

The above base oils may he used individually or in combinations thereof, wherever miscible or wherever made so by the use of mutual solvents.

When used as rust inhibitors the alkylbutyrolactone-aacetic acids can be used in oils of lubricating viscosity in amounts of 0.1% to 10% by weight, preferably 0.25% to by weight.

The preparation of the alkylbutyrolactone-a-acetic acids described herein is illustrated in the following examples.

EXAMPLE 1.PREPARATION OF THE METHYL ESTER OF POLYBUTENYLBUTYROLACTONE-oc- ACETIC ACID A mixture of 93.8 g. (0.1 mole) of a polybutene (molecular weight of about 840) in 100 ml. heptane, 225 g. (1 mole) of dimethyl bromosuccinate, and 1.46 g. (0.01 mole) of di-t-butyl peroxide was charged to a rocker bomb, and the vessel purged with nitrogen. The reaction mixture was heated at 130 C. with agitation for 5 hours, then cooled to room temperature, and the methyl bromide vented to the atmosphere. The reaction mixture was vacuum distilled to remove the heptane and the unreacted dimethyl bromosuccinate.

Infrared analysis of the product showed the spectrum characteristics of the lactone (1780 cmr and the ester (1735 cmf EXAMPLE 2.PR'EPARATION OF THE METHYL ESTER OF DECYLBUTYROLACTONE-oc-ACETIC ACID A mixture of 98.5 g. (0.438 mole) of dimethyl bromosuccinate, 14.7 g. (0.0875 mole) l-dodecene, 1.0 g. (0.00875 mole) of acetyl peroxide in 9 ml. of dimethyl phthalate, and 50' ml. benzene was heated with agitation for 4 hours at 90 C. The benzezne and unreacted dimethyl bromosuccinate were removed by distillation at reduced pressure, followed by heating the residual yellow oil for minutes at 195-205 C. at an absolute pressure of 2 mm. Hg. The final residue was crystallized from an ether-pentane solvent, resulting in a light brown waxy solid having a melting point range at 3237 C. Infrared analysis of this product showed the spectrum characteristics of a lactone at 1775 cm? and the ester at 1735 CIILTI.

Further purification resulted in white crystals which had a melting point of 4345 C. Elemental analysis showed:

Calculated: 68.40% C., 10.14% H. Found: 68.35% C., 8.19% H.

The following equations exemplify the reactions of Example 2:

CH3 CH2 0CH=CH2 BrCHOOCI-Ia CHzCOOCI-Is I CH3(CH2)9CHCH2CI'ICOOCHs 1 Heat CII3(CH2)DGIICH2OI-ICOCOH3 OHtCOOGI-Ia The methyl ester of decylbutyrolactone-a-acetic acid prepared above was converted to the corresponding acid. A mixture of 2 g. of lactone ester, 50 ml. of 96% sulfuric acid and 50 g. of ice were stirred and warmed to 100 C., at which temperature the stirring was continued for about 3 hours. The mixture was cooled until the lactone acid crystallized on top of the sulfuric acid. The lactone acid was then extracted with diethyl ether using ten separate ml. extractions. The combined ether extracts were chilled in a Dry Ice-acetone bath. The extracts were then filtered to separate the lactone acid in the form of white crystals. Infrared analysis of a melt-smear of the white crystals gave the expected peaks of a lactone acid. Further recrystallization of the white crystals from ether yielded a sample having a melting point of 104 C., the analysis of which showed a percent carbon of 67.73 and percent hydrogen of 9.68 corresponding to theoretical values of 67.61 and 9.86, respectively.

The lactone acids of the invention are useful themselves as rust inhibitors in lubricating oil compositions in the formulations described above. However, another important feature is their utility as intermediates for reaction with various amines to provide effective nitrogen containing ashless detergents for lubricants.

The following example illustrates the use of the alkylbutyrolactone-a-acetic acids as intermediates in the formation of the corresponding amides which are effective as detergents in lubricating oil compositions.

EXAMPLE 3.-PREPARATION OF TETRAETHYL- ENE PENTAMINE AMIDE OF AN ALKYLBU- TYRLACTONE-u-ACETIC ACID DERIVED FROM A BUTYLENE POLYMER An alkylbutyrolactone-a-acetic acid was prepared from a butylene polymer having -a molecular weight of about 850. A 40% solution of this lactone in a hydrocarbon oil was reacted with an ethylene amine condensation product having a molecular weight corresponding to tetraethylene pent-amine.

A mixture of 76 g. (0.4 mole) of this tetraethylene pentamine and 1218 g. (0.50 mole) of the the product of the alkylbutyrolactone-a-acetic acid was blended with agitation at 150 C. for one hour, allowed to cool, then stand for 36 hours at room temperature. The mixture 7 was then reheated at 150 C. for 1 hour.

Infrared analysis showed a band at 1650-1700 cm. due to the amide carbonyl group, and a band at 1775 cm." due to the butyrolactone carbonyl group.

Table I hereinbelow presents data obtained with several illustrative tests of derivatives. Tests B and C are lubricating oil compositions containing 1% by weight of the amide obtained in Example 3 hereinabove in combination with metal dithiophosphates. Tests D and E are lubricating oil compositions containing 1.5% of amides derived from triethylene tetramine and diethylene triamine, respectively. The concentration of the dithiophosphates is expressed in millimoles per kilogram of finished composition (based on the metal), that is, mM./kg.

Dithiophosphate A was a zinc salt of a mixed dialkyl dithiophosphate wherein one of the alkyl radicals contained 4 carbon atoms and the other alkyl radical contained 5 carbon atoms. Dithiophosphate B was a zinc dialkylphenyl dithiophosphate.

The test was made in a Caterpillar L1 engine according to Supplement I conditions for a period of 120 hours as described in the Coordinating Research Council Handbook, January, 1946.

The PD Nos. refer to the piston discoloration rating. After the engine test, the three piston lands are examined visually. To a piston skirt which is completely black is assigned a PD number of 800; to one which is completely clean, a PD number of 0; to those intermediate between completely black and completely clean are assigned PD numbers intermediate in proportion to the extent and degree of darkening.

The GD Nos. refer to the percentage deposits in the piston ring grooves; a 0 evaluation being a clean groove; and a number of being a groove full of deposits.

The base oils were California SAE 30 base oils.

1 These te t results were obtained in a Caterpillar L-l te t under the MIL-L2104 conditions. Thus, under the more severe Supplement-1 conditions, these GD Nos. would be considerably higher.

Table II hereinbelow presents data obtained in an FL-2 test, using a 6-cylinder Chevrolet engine operating at 2500 rpm. for a period of 36 hours, which test is fully described in a Coordinating Research Council bulletin titled Research Technique for the Determination of the Effects of Fuels and Lubricants on the Formation of Deposits During Moderate Temperature Operation" (1948).

The piston varnish rating is a visual observation of the amount of varnish on a piston skirt, with 10 being the maximum rating for a perfectly clean piston, and 0 being the rating of a piston fully covered with black varnish. This piston varnish rating correlates with road performance in automobiles.

The total rating is the overall deposit rating of the engine, with the rating values ranging from 0, the poorest value, to 100, the top value. These figures indicate the percentage rating for the engine.

The base oil was an SAE 30 base oil.

The succinirnide and the dithiophosphates were the same as those described for Table I hereinabove.

In an L-38 strip corrosion test, the copper strip weight loss was only 15.5 milligrams when using a petroleum base oil containing 6% by weight of the amide prepared as in Example 3 hereinabove.

Table III hereinbelow presents data obtained in an L38 engine test, using a l-cylinder CLR engine. The test period was for 40 hours.

T able III Additive:

Amide (Example 3), wt. percent 2.0 Dithiophosphate A, mM./kg. 10 Dithiophosphate B, mM./kg 2 Test results: Bearing weight loss (mgs) 55.4

wherein R R and R are selected from the group consisting of hydrogen and alkyl radicals having a total of from 10 to 300 carbon atoms.

2. A lubricating oil composition comprising a major proportion of an oil of lubricating viscosity, and from 0.25% to 5% by weight of an alkylbutyrolactone-aacetic acid of the formula wherein R R and R are selected from the group consisting of hydrogen and alkyl radicals having a total of from 10 to 300 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 6/1958 Nemec 260343.6 11/1964 Prill et al 260343.6

OTHER REFERENCES Kharasch: J our. American Chem. Soc. (1948), pages 1055-1059.

DANIEL E. WYMAN, Primary Examiner.

W. H. CANNON, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2839538 *Aug 26, 1953Jun 17, 1958Rohm & HaasSubstituted butyrolactones
US3155685 *Jan 4, 1960Nov 3, 1964Monsanto CoPreparation of ester lactones
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US4081456 *Feb 20, 1976Mar 28, 1978Mobil Oil CorporationBis-lactam derivatives
US4167514 *Jun 13, 1977Sep 11, 1979Exxon Research & Engineering Co.Heterosubstituted alkyl lactone acids, esters and amides
US4302395 *Jul 11, 1980Nov 24, 1981Exxon Research & Engineering Co.Lactone oxazolines as oleaginous additives
US4329286 *May 4, 1979May 11, 1982Mobil Oil CorporationHydroxyamide acid products and butyrolactone and butyrolactam products
US4539127 *Feb 3, 1982Sep 3, 1985Mobil Oil CorporationHydroxyamide acid products and butyrolactone and butyrolactam products
US5447954 *May 5, 1992Sep 5, 1995Smithkline Beecham P.L.C.Phenylderivate as inhibitors of ATP citrate lyase
US5779742 *Aug 8, 1996Jul 14, 1998The Lubrizol CorporationAcylated nitrogen compounds useful as additives for lubricating oil and fuel compositions
US5856279 *May 19, 1998Jan 5, 1999The Lubrizol CorporationAcylated nitrogen compounds useful as additives for lubricating oil and fuel compositions
US5859264 *Mar 11, 1996Jan 12, 1999Croda International, PlcExplosive compositions
US6020500 *Aug 22, 1995Feb 1, 2000The Lubrizol CorporationHydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
US6114547 *Jan 19, 1999Sep 5, 2000The Lubrizol CorporationHydroxy-substituted monolactones and use thereof as intermediates for preparing lubricating oil and fuel additives
US6207839Aug 5, 1998Mar 27, 2001The Lubrizol CorporationProcess for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives
US6268317 *Oct 27, 1998Jul 31, 2001Matsushita Electric Industrial Co., Ltd.Working fluid for refrigerating cycle equipment and the refrigerating cycle equipment using the same
DE2740535A1 *Sep 8, 1977Mar 30, 1978Exxon Research Engineering CoKohlenwasserstoffloesliche alkyllaktonoxazoline, verfahren zu ihrer herstellung und ihre verwendung in kohlenwasserstoffen als antirost- und/oder schlammdispergiermittel
EP0291458A1 *May 6, 1988Nov 17, 1988Ciba-Geigy AgCorrosion inhibiting composition
EP0759443A2 *Aug 20, 1996Feb 26, 1997The Lubrizol CorporationHydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
EP0823471A1 *Aug 4, 1997Feb 11, 1998The Lubrizol CorporationAcylated nitrogen compounds useful as additives for lubricating oil and fuel compositions and intermediates useful for preparing same
WO1993003121A1 *Jul 15, 1992Feb 18, 1993The Lubrizol CorporationImproved lubricating compositions and additives useful therein
WO1993022304A1 *Apr 29, 1993Nov 11, 1993Smithkline Beecham PlcPhenylderivate as inhibitors of atp citrate lyase
WO1996028436A1 *Mar 11, 1996Sep 19, 1996Croda International PlcExplosive compositions